Disazo and polyazo dyestuffs



United States Patent 2,721,864 DISAZO AND .POLYAZO DYESTUFFS Philippe; Grandjean, Basel, and Walter Wehrli, Riehen,

Switzerland, assignors to Sandoz A. G., Basel, witz erland, a Swiss firm V No Drawing. Application March 2, 1953,

Serial No. 339,896 Claims priority, application Switzerland March 7, I952 6 Claims. (Cl. 260-173) The present invention relates to new disazo and polyazo dyestuffs and to the preparation thereof.

Dyestuffs which yield yellow, orange and brown shades in textile dyeings are known. However, such dyestuffs, when they are characterized by good fastness to light, are frequently bound up with poor dischargeability or, when their dischargeability is good, suffer from poor fastness to light. Their dyeings are frequently also impaired by treatments incidental to creaseproofing.

A primary object of the present invention is the embodiment of a new series of dyestufis of the said class yellow, orange, red-brown and brownwhich are characterized by the fact that, in addition to the purity of shade of the dyeings produced therewith, such dyeings possess both good fastness to light and good dischargeability, and are also unimpaired by creaseproofing treatments.

This and other objects which will hereinafter appear are realized by the present invention according to which, briefly stated, the desired dyestuffs are prepared by condensing two mols of an aminoazo compound of the formula:

(I) R1aZOR2XNH2 wherein R1 stands for a radical of the pyrene series, R2

stands for a radical of the benzene series, X stands for a simple bond or one of the bridge groupings:

and

yellow, orange, red-brown and brown shades.

wherein each Z stands for C1 or Br, and A stands for H,

Cl, Br or CH3.

Alternatively, one mole of a dicarboxylic acid halide of Formula II may be condensed with two mols of a mixture, composed as desired, of aminoazo compounds of Formula I, or with two mols of a mixture, composed as desired, of an aminoazo compound of Formula I and of a non-metallizable aminomonoazo or aminodisazo compound of any desired composition.

In each case, however, the reactants must be so selected that the resultant disazo or polyazo dyestuff contains a sufiicient number of solubilizing groups, such as example as an alkali metal hydroxide, an alkali metal carbona'te, an alkaline earth metal oxide, an alkaline earth metal carbonate, an alkali metal acetate, or a suitable organic tertiary amine such as N,N-dimethylaminobenzene, being added at the beginning or during the course of the reaction.

Suitable dicarboxylic acid halides of Formula II comprise the dichlorides and dibromides of fumaric acid, maleic acid, methylfumaric acid, methylmaleic acid, chlorofumaric acid and bromofumaric acid.

The new disazo or polyazo dyestufls, correspond to the general formula wherein A stands for H, Cl, Br or CH3, one R stands for the grouping:

and the other R stands for the identical Grouping III or for the grouping:

In the foregoing Formulae III and IV, X may be a simple bond or may be one of the bridging radicals, substituted or unsubstituted, of the formulae:

n is one of the integers l and 2, R1 is a radical of the pyrene series, R2 is a radical of the benzene series which may be substituted by lower alkyl (e. g. methyl, ethyl, propyl, butyl, etc.), lower alkoxy (e. g. methoxy, ethoxy, propoxy, etc.), or acylamino (e. g. acetylamino, propionylamino, etc.), and each of R3, R4 and R5 is a radical of the benzene or of the naphthalene series which may be substituted by halogen (e. g. Cl, Br, etc.), lower alkyl, lower alkoxy, acylamino or nitro. Moreover, the dyestuds must comprise a total of at least three solubilizing (-e. g. SOaH and/ or COOH) groups.

The said new dyestuffs according to the present invention dye cotton and fibers of regenerated cellulose in The dyeings are distinguished by their high fastness to light and by their generally very good dischargeability. They are very stable to creaseproofing treatments. In those cases where the aminoazo components employed are not identical, the products comprise a mixture of asymmetrical dyestuff with the corresponding two symmetrical dyestuffs.

The following examples illustrate the invention, but the latter is not intended to be restricted to the particular condensation conditions recited therein. In these examples, the parts are by weight.

and

Example 1 495 parts of the aminoazo compound prepared 'by coupling diazotized 3-aminopyrenedisulfonic acid '(which may be in the form of a mixture of 3-aminopyrene-5,8- disulfonic acid and 3-an1inopyrene-5,l0-disulfonic acid, obtained in known manner by sulfonating 3-aminopyrene) with 1-amino-3-methylbenzene, are dissolved in water at room temperature, neutrality being maintained by the addition of aqueous sodium hydroxide solution. Into the thus-obtained solution, there are simultaneously added, dropwise and while stirring thoroughly, a solution of 76.5 parts of fumaric acid dichloride and parts of benzene as well as a sufiicient quantity of aqueous sodium carbonate solution to maintain the reaction weakly alkaline throughout. After all the fumaric acid dichlo- 3 ride has been added, stirring of the solution is continued until no free amino group is detectable. Thereupon the resultant new dyestufi is separated from the warm solution with the aid of sodium chloride, after which it is filtered E and dried. It corresponds to the formula SOaH .dimethylbenzene, 1-amino-3-formylaminobenzene, l-amino-3-acetylaminobenzene, l-amino-3-propionylaminobenzene, l-amino-3-benzoylaminohenzene, 1-amino-2-methoxybenzene, 1-amino-2-ethoxybenzene, 1-amino-3-methoxybenzene, 1-amino-2-methoxy-S-methylbenzene, 1-amino-2 methoxy S-acetylaminobenzene, l-amino 2,5-dimethoxybenzene or l-amino-2,5-diethoxybenzene. In the case, for example, of 1-amino-Z-methoxy-S-methylbenzene, the resultant dyestufr corresponds to the formula OaH OCH:

If the fumaric acid dichloride is replaced by fumaric acid dibromide, the identical dyestufi is obtained in each of the described instances.

4 Example 2 254.5 parts (0.5 mol) of the aminoazo compound prepared by coupling diazotized 3-aminopyrenedisulfonic acid with 1-amino-2,S-dimethylbenzene and 262.5 (0.5 mol) of the aminoazo compound prepared by coupling diazotized S-aminopyrenedisulfonic acid with 1-amino-2- methoxy-S-methylbenzene are together dissolved in water, neutrality being maintained by the addition of an aqueous sodium hydroxide solution, after which condensation is carried out according to the data of Example 1 with 76.5 parts (0.5 mol) of fumaric acid dichloride. After isolation, the resultant dyestuif mixture is a reddish yellow powder and dyes cotton and fibers of regenerated cellulose in orange shades of very good dischargeability and fastness to light. The asymmetrical componentv thereof corresponds to the formula HOaS OCHB

Dyestufis of similar properties are obtained when, in the starting aminoazo compounds, the 1-amino-2,5-dimethylbenzene and/or the l-amino-Z-methoxy-S-methylbenzene are/is replaced by one of the amines enumerated in Example 1, provided that the two starting dyestutfs are not identical.

If the two mixture components are condensed in other mol relationships with fumaric acid dichloride, as for example in the proportion of 0.4:O.6 or 0.75 :0.25, the products are more reddish or more yellowish dyestuffs with equally good properties.

If the fumaric acid dichloride is replaced by maleic acid dichloride or maleic acid dibromide or by methylfumaric acid dichloride or methylfumaric acid dibromide, cotton dyestufis of similar properties are obtained.

Example 3 614 parts of the aminoazo compound, obtained by coupling diazotized 3-aminopyrenedisulfonic acid with 1-amino-3-methylbenzene, condensing the resultant intermediate with 4-nitrobenzoyl chloride, and then reducing the nitro group to the amino group, are dissolved in water at room temperature, neutrality being maintained by the addition of aqueous sodium hydroxide solution, after which condensation is carried out according to the data of Example 1 with 76.5 parts of fumaric acid dichloride. After isolation, the resultant disazo dyestufl is a yellowbrown powder, which corresponds to the formula NEH NH-O C NH-O 0-4311:

and dyes cotton'an'd fibers of regenerated cellulose in Example golden yellow shades of excellent light-fastness. 262 5 v v 1 parts (0.5 mol) of the ammoazo compound massi staircases? sesame by with p 1-ammo-Z-methoxy-S-methylbenzene and 225.5 parts amino-B-methylbenzene is replaced by one of the amines 5 (05 mol) of the aminoazo compound prepared by of the benzene serles enumerated m Example 1 and/or, coupling diazotized 2 aminonaPht-halehe 6- 8disulionic s; t;ztnlzszntfhtzzxxrzizzl ait:the? y r f g gj: g m so ve in water W1 e a men 0 aqueous so ium benzoyl group or the S'ammO'4'methOXYbeHZOYI group hydroxide solution, after which condensation is carried Example 4 out according to the data of Example 1 with 76.5 parts (0.5 mol) of fumaric acid dichloride. After isolation, the resultant dyestuif mixture is a red-brown powder, which dyes cotton and fibers of regenerated cellulose in 313 parts (0.5 mol) of the aminoazo compound, obtained by coupling diazotized 3-aminopyrenedisulfonic acid with 1-amino:2,5-dimethylbenzene, condensing the resultant intermediate with 3-nitrobenzoyl chloride, and Orange Shades of excellent dischargeability and lightthen reducing the nitro group to the amino group, and fastness. The asymmetrical component corresponds to 262.5 parts (0.5 mol) of the aminoazo compound prethe formula SOgH v OCH; 0 CH: .BOiH H038 N=N NHOCCH=CHC Q-NHGNQQ- 6H; CH: 301E pared by coupling diazotized 3-aminopyrenedisulfonic 3O Dyestuffs of similar properties are obtained when, on acid Y- fl i the one hand, the 3-aminopyrenedisulfonic acid in the first gether dissolved .neutra in water Wlth the addition of component. the mixture i l d by 3-aminopyreneaqueous sodium hydroxide solution, after which conden- Sation is carried out acording to the data of Example 1 4-monosulfomc acid or by 3-am1nopyrene-8-monosulfon1c with 76.5 parts 0.5 mol) of fumaric acid dichloride. i or y 3-amin0pyrene-10-mon0sulf0nic i and/or After isolation thereof, the resultant dyestutf mixture is th 1-ami o-2-meth xy -5-methylbenzene by one of the an orange powder.whlch dyes and fibers of amines of the benzene series mentioned in Example 1 generated cellulose in orange shades of very good fastness to light. The asymmetrical component corresponds to and/or on the other hand in the second component of the formula 40 the mixture, the 2-aminonaphthalene-6,8-disu1fonic acid SOsH HOaS

Dyestufis of similar properties are obtained when, .on v is replaced by 2-aminonaphthalene-4,8-disulfonic acid or the one hand, the 3-aminobenzoyl group in the first comby Z-aminonaphthalene-S,7-disulfonic acid and/or the 1- ponent of the mixture is replaced by the 4-aminobenzoyl amino-2-methoxy-S-methylbenzene by one of the amines group or the 4-amino-3-methylbenzoyl group or the 3- of the benzene series enumerated in Example 1. The dye amino-4-methoxybenzoyl group and/ or, on the other with 3-aminopyrene-4-monosulfonic acid and Z-aminohand, the second component of the mixture is replaced by naphthalene-4,8-disulfonic acid corresponds to the one of the aminoazo compounds mentioned in Example 1. formula r q CH: OCH; SIOIH HOIS pared by coupling diazotized 3-aminopyrenedisulfonic acid with 1-amino-2,5-dirnethylbenzene and 237.5 parts (0.5 mol) of the aminoazo compound prepared by coupling diazotized 4'-amino-1,1-azobenzene-3',4-disulfonic acid with l-amino-B-methylbenzene are dissolved in water with the addition of sodium hydroxide, after which condensation is carried out according to the data of Example 1 with 76.5 parts (0.5 mol) of fumaric acid dichloride.

'8 lent dischargeability and fastness to light. .The asym; metrical compound thereof corresponds to the formula I Dyestufis with similar properties are obtained when, on the one hand, the first mixture component is replaced by one of the aminoazo or aminobenzoylaminoazo compounds enumerated in Examples 1 and 3 and/ or, on the other hand, the second mixture component is replaced by any other. desired non-metallizable aminoazo compound. The following table exemplifies a representative number of the numerous possible variations, the procedure in each case being analogous to that set forth in After isolation, the resultant dyestufii mixture is an 25 the preceding examples:

shadaFcir Cotgm an ero e- Exarnple No. First Mixture Component Second Mixture Component generated Caulk 'lose.

7 3-aminopyrenedisulfon1c acid 4-amino-1,1-azobenzene-3,4-disul orange.

1-amino-2-methoxy-5-methylbenfonic acid 1-amino-3- zeue. methylbenzene, condensed with 4- nitrobenzoyl chloride and reduced to the aminobenzoylamino-disazo compound. 8 2 aminonaphthalene 6,8 disulfonic reddish orange.

acid aminobenzene 1-amino-3-methylbenzene.

9 3-aminopyrenedisulionic acid 2-aminonaphthalene-4,8-disulionic red.

1-amln0-2-methoxy-5-acetyiaminoacid 1-amin0-3-ruethylbenbenzene. zene l-amino-2-methoxy-5- methylbenzene. 10 3-aminopyrenedisulionic acid 4-amino-1,1-azobenzene-3,4-disulreddish yellow.

Lamina-2,S-dimethylbenzene. ionic acid condensed with 4-nitrobenzoyi chloride and reduced to the aminobenzoylaminoazo compound. 11 B-aminopyrenedisulionic acid 2-arninonaphthalene-4,8-disulfonic yellowish orange. l-amino-B-methylbenzene. acid 1-amino-3-methylbenzene 1-amino-3-methylbenv zene. 12. 3-aminopyrencdisulfonic acid 4-amino-1,1-azobenzene-3,4-disu1- orange-red.

' 1-amino-2-methoxy-5methy1benionic acid 2-amino-5-hyzene. droxynaphthalene-7-sulf0nlo acid. 13 3-aru1nopyrenedisulionic acid l-aminobenzene--sulfonicacid orange-brown.

l-amino-Z-methyoxybenzene. 1-aminonaphthalene-7sulf0nic acid l-amino-B-methylbenzene. 14 3-arninopyrened1sulionic acid 1-amino-2,4-dichlorobenzene-6-sulyellow-brown.

l-amino-Ei-methylbenzene. tonic acid l-aminonaphthalenc-fi-sulfomcacid aminobenzene. 15 do 1-amino-4-bromobenzene-2-sulfonic red-brown.

acid l-aminonaphthalenefi-sulfonic acid Lamina-2- methoxy-5-formylaminobenzene. do 1-amino-Z-carboxybenzene-5-sulfonic yellow-brown.

acid 1 -aminonaphthalene l-amtno-S-benzoylamino- I benzene.

orange-brown powder which dyes cotton and fibers of regenerated cellulose in brownish orange shades of excel- SOIH O CH:

H015 N=N games r and that according to Example corresponds to the formula Example 17 100 parts of cotton are entered at 80 into a dyebath which contains 1 part of anhydrous sodium carbonate, 0.5 part of the dyestuff obtainable according to Example 2 and 2000 parts of water. The dyebath is heated slowly to boiling, after which 20 parts of anhydrous sodium sulfate are added and the mixture allowed to cool slowly to about 70. The material is removed, rinsed with cold water and then dried. An orange dyeing is obtained which has good fastness to washing and excellent lightfastness and dischargeability. It tolerates creaseproofing treatments very well.

In similar manner, dyeings may be obtained with the.

dyestuffs of the other examples. Having thus disclosed the invention what is claimed is:

1. Disand polyazo dyestufls which correspond to the v wherein A stands for a member selected from the group consisting of hydrogen, chlorine, bromine and methyl, one R stands for the radical of the formula and the other R stands for a member selected from the group consisting of radicals of the formulae and (Ra-N=N-)n 1R4-azoR5-X-NH, wherein azoand -XNH- stand in para-position to each other, X stands for a member selected from the group consisting of a simple linkage, and of the radicals radicals, n is one of the integers 1 and 2, R1 stands for a radical of the pyrene series, Ra stands for a member selected from the group consisting of phenyl, lower alkyl-substituted phenyl, lower alkoxy-substituted phenyl and carboxyacylaminophenyl, each of R3, R4 and Rs stands for a member selected from the group consisting of unsubstituted and substituted phenyl and naphthyl radicals, the substituents being chosen from the group consisting of chlorine and bromine atoms, lower alkyl, lower alkoxy, carboxyacylamino' and nitro groups, said dyestulfs containing at least three water-solubilizing groups selected from the class consisting of sulfonic acid and 'carboxylic acid groups.

Y 2. .I'he'disazo dye which corresponds to the formula and 3. The disazo dye which corresponds to the formula 11 12 4. The disazo dye which corresponds to the formula a 501K HOaS CH; 0H: 5. The trisazo dye which corresponds to the formula BOzH H 6. The disazo dye which corresponds to the formula ooHQ- I 1cm S0311 no.5 N=NNH-O ocH=oH-0 O-NfiQN: 1 CH; I OH: 803E References Cited in the file of this patent I UNITED STATES PATENTS 2,104,595 Schirm Jan. 4, 1938 2,212,590 Delfs Aug. 28, 1940 2,617,797 k Anderau Nov. 11, 1952 2,646,338 Kappeler et a1 July 21, 1953 FOREIGN PATENTS 504,489 Belgium July 31, 1951 

5. THE TRISAZO DYE WHICH CORRESPONDS TO THE FORMULA 